CN103214379B - Preparation method of fluorocarbon/hydrocarbon mixed type cation surface active monomer - Google Patents
Preparation method of fluorocarbon/hydrocarbon mixed type cation surface active monomer Download PDFInfo
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Abstract
The invention provides a preparation method of fluorocarbon/hydrocarbon mixed type cation surface active monomer, and the structural formula is shown in the description. The invention has the advantages of simple synthesis steps and products purification, high yield, safety usage and convenient storage. The fluorine containing surface active monomer can be copolymerized with a plurality of monomers for preparing various functional large molecules, and is widely applied to the fields of oil field exploitation, coating, fire-fighting, printing, electroplate, daily use chemical industry, medicine, etc.
Description
Technical field
The present invention relates to a kind of preparation method of surface active monomer, be specifically related to a kind of preparation method of fluorine-containing cationic surface active monomer, particularly a kind of preparation method of the quaternary surface active monomer that simultaneously contains perfluoroalkyl and hydrocarbon hydrophobic grouping.
Background technology
Fluorine carbon/hydrocarbon mixed surfactant has fluorine carbon and hydrocarbon hydrophobic grouping simultaneously, there is higher surfactivity, stability and gathering performance, can form the aggregate of various structures, as the vesica of similar human brain, Micelle-like Nano-structure of Two and heterogeneous separation micella, can be applied to numerous areas, as pharmaceutical carrier, nanometer microreactor and gene conveying etc., become one of focus of current research.Surface active monomer, or title polymerisable surfactant (surfamer), be a kind of functional surface promoting agent, this surfactant molecule not only comprises amphiphilic structure (hydrophilic base and hydrophobic tail base), and also has polymerisable pair of key group.This special molecular structure is given the physicochemical property of their uniquenesses: (1) is similar to conventional surfactants, and they have surfactivity; (2) similar to vinyl monomer, they can be caused polymerization reaction take place by initiator.Amphipathic and the polymerizability of surface active monomer makes them be widely used at a lot of sciemtifec and technical spheres.For example, polymerizable surface active monomer can be for the preparation of bionical vesica, thereby prepares functional centrosome; Can build for the synthesis of functional inorganic nano material or inorganic-organic nanocomposite soft template used; Can also improve emulsion polymerization as polymerisable emulsifying agent.Fluorine-containing surfactants monomer is a kind of special surface reactive monomer of introducing fluorine carbon hydrophobic grouping.Compared with hydrocarbon surface active monomer, fluorine-containing surfactants monomer has high surface, the physical and chemical performance that high heat-resistant stability and high chemical stability etc. are excellent; The Polyacrylamide Hydrophobic Associating Derivatives that itself and acrylamide copolymerization are obtained shows good thickening effectiveness and temperature resistant antisalt ability.
At present, domestic many researchists are studied the preparation method of fluorine-containing surfactants monomer, normally first synthesize the perfluoroalkyl iodo alkane of 6～10 carbon atoms, then the synthetic fluoro-containing intermediate (as alcohol, mercaptan, amine, acid amides, sulfonic acid fluoride etc.) that is easy to introduce various hydrophilic radicals, finally introduces hydrophilic radical and polymerizable groups and makes various fluorine-containing surfactants monomers.But this preparation method exists many weak points, as synthesizing final product---the required step of fluorine-containing surfactants monomer is various, complicated operation, reaction conditions is harsher, product purification difficulty, reaction yield is lower etc.In addition, there is not yet open research report about fluorine carbon/hydrocarbon mixed type cation surface active monomer synthetic domestic.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, the preparation method of a kind of fluorine carbon/hydrocarbon mixed type cation surface active monomer is provided, wherein, compound IV is a kind of fluorine carbon/hydrocarbon mixed type cation surface active monomer that the present invention synthesizes.
Synthesis step is as described below:
Step (i), utilizes tert-Butyl dicarbonate (Boc acid anhydrides) to N, and the amino of N-dimethyl-ethylenediamine is protected, and amino is changed into the amide group that chemical property is more stable.
Step (ii); the N that amino has been protected by Boc; the bromo-1-hexene of N-dimethyl-ethylenediamine and 6-carries out quaterisation, after reaction finishes, and removal of solvent under reduced pressure; add anhydrous diethyl ether; ice bath stirs 2～12 hours, separates out white solid, suction filtration; obtain white solid powder, i.e. Compound I.
Step (iii), utilizes the ether (HCl-Et of hydrochloric acid
2o) saturated solution is to the de-Boc of Compound I, and after reaction finishes, removal of solvent under reduced pressure, adds anhydrous diethyl ether, and ice bath stirs 2～12 hours, separates out white solid, and suction filtration, obtains white solid powder, i.e. Compound I I.
Step (iv); under initiator dibenzoyl peroxide (BPO) effect; iodine and ethanoyl are then sloughed in perfluoro-hexyl iodide alkane and allyl acetate generation addition reaction under the effect of potassium hydroxide (KOH), filter; filtrate decompression distillation; collecting 77～80 ℃/40mmHg cut, is colourless liquid, i.e. compound III; 3-(perfluor n-hexyl)-1,2 epoxy prapane.
Step (v), carries out ring-opening reaction by Compound I I and compound III, and removal of solvent under reduced pressure adds anhydrous diethyl ether precipitation, obtains compound IV, is yellow thickness lotion.
In above-mentioned preparation method, the described N of step (i), the mol ratio of N-dimethyl-ethylenediamine and tert-Butyl dicarbonate can be 1: (1.1～1.5), solvent can be N, dinethylformamide (DMF), acetone, methyl alcohol or ethanol, N, N-dimethyl-ethylenediamine can be 1 with the massfraction ratio of described solvent: (16～25), temperature of reaction can be 25～40 ℃, reaction times can be 0.5～2 hour, feeding mode is that tert-Butyl dicarbonate is dissolved in appropriate solvent, in 0.5～1 hour, dropwise splash into N, in the reaction system that N-dimethyl-ethylenediamine exists, reaction is carried out under nitrogen atmosphere.
In above-mentioned preparation method, step (ii) finishes directly to carry out afterwards in step (i) reaction, utilizes one kettle way synthetic compound I.N, the mol ratio of the bromo-1-hexene of N-dimethyl-ethylenediamine and 6-can be 1: (1.1～1.3), no longer add solvent, temperature of reaction remains unchanged, reaction times can be 24～72 hours, feeding mode is that bromo-6-1-hexene was dropwise splashed in the reaction system of step (i) in 0.5～I hour, and reaction is carried out under nitrogen atmosphere.
In above-mentioned preparation method, the described reaction solvent of step (iii) is methyl alcohol, Compound I and can be 1 with the massfraction ratio of solvent: (4～7), HCl-Et
2the volume ratio of O saturated solution and solvent is 1: (2.5～5), temperature is 10～25 ℃, and the reaction times can be 6～12 hours, and feeding mode is by HCl-Et
2o saturated solution dropwise splashed in the reaction system of Compound I existence in 0.5～1 hour.
In above-mentioned preparation method, the mol ratio of the described perfluoro-hexyl iodide alkane of step (iv) and allyl acetate is 1: 1, by the two mix and blend, solution to be mixed keeps several minutes after being warming up to 95 ℃, add afterwards BPO, the mol ratio of BPO and perfluoro-hexyl iodide alkane can be 1: (50～100), and behind question response steep temperature rise to 160～170 ℃, be cooled to 120～130 ℃, keep 30～60 minutes.Then in above-mentioned reaction system, add successively normal hexane and KOH, normal hexane is solvent, and can be (1.5～2) with the massfraction ratio of perfluoro-hexyl iodide alkane: 1, the mol ratio of KOH and perfluoro-hexyl iodide alkane can be (2.5～3): 1, reaction times can be 4～6 hours, and temperature is 70～80 ℃.
In above-mentioned preparation method, the mol ratio of the described Compound I I of step (v) and compound III can be 1: (3～5), solvent can be methyl alcohol or ethanol, Compound I I can be 1 with the massfraction ratio of described solvent: (100～120), temperature of reaction is can 80～90 ℃, reaction times can be 5～7 days, and described reaction is carried out under nitrogen atmosphere.
Preparation method provided by the invention has the following advantages:
1, raw material is easy to get, and synthesis step and product purification are simple, and yield is high, uses safety, and it is convenient to store.
2, utilize one kettle way synthetic compound I, save the step of purification intermediate product, and product postprocessing is simple, purity is high, and yield is high.Because the reaction of amino being protected with Boc acid anhydrides is generally all very easily carried out, and the relative N of Boc acid anhydrides, N-bis-Shen base quadrols are excessive, therefore can guarantee N, N-dimethyl-ethylenediamine reacts completely.The N that amino is protected by Boc completely; N-dimethyl-ethylenediamine and the excessive bromo-1-hexene of 6-carry out quaterisation, obtain mono-quaternaries, utilize itself and other dissolubility difference of compound in ether; just can obtain pure mono-quaternaries product, so later stage product purification is simple.
3, simple and convenient to the operation of the de-Boc of Compound I, and product postprocessing is simple, and purity is high, and yield is high.Because-NHBoc is responsive especially to acid, in acid, be very easily dissociated into iso-butylene and carbonic acid gas, so de-Boc reaction is simple and convenient, later-stage utilization Compound I I and the dissolubility difference of other compounds in ether with regard to separable go out pure product.
4, compound III is synthetic simple, and product collection is convenient, and purity is high.Compare the reaction process of other synthetic fluoro-containing intermediates (as alcohol, mercaptan, amine, acid amides, sulfonic acid fluoride etc.) that are easy to introduce various hydrophilic radicals, this kind of synthetic method is simple to operate, and one kettle way can complete, reaction conditions gentleness, easy to control, toxicity is low, and yield is high.5, the synthesis step of fluorine-containing surfactants monomer I V (v) is simple to operate, and purifying is convenient, and product yield is high, and purity is high.Due to excessive 2～4 times of compound III relativization compound II, therefore can guarantee that Compound I I reacts completely; And secondary amine steric hindrance on fluorine-containing surfactants monomer I V is larger, continue to occur ring-opening reaction difficulty especially, so the primary amine on Compound I I can only change into secondary amine, and be difficult to change into tertiary amine or quaternary ammonium ion, nuclear-magnetism result also proves so, therefore reaction finishes to only have product IV polarity larger in rear system, utilizes itself and the dissolubility difference of low polar compound in ether, can isolate pure product IV.
6, whole building-up process is temperature required lower, and most of step normal temperature just can complete, and simple to operate easy to control, energy consumption is low, is suitable for industry extensive synthetic.
7, synthetic fluorine-containing surfactants monomer is a kind of fluorine carbon/hydrocarbon mixed type quaternary surfactant, is widely used, as makes hair conditioner, fabric softener, sterilant, pharmaceutical carrier, gene delivery carrier etc.
8, the fluorine-containing surfactants monomer of preparation can be made various functional macromolecules by emulsifier-free emulsion polymerization with various of monomer, save complicated product purification process, can be widely used in oil-field development, coating, fire-fighting, printing, plating, daily-use chemical industry, medicine and other fields.
Above-mentioned various features shows, the present invention is suitable for suitability for industrialized production, and is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the concrete synthetic route of fluorine carbon/hydrocarbon mixed type cation surface active monomer.
Fig. 2 is Compound I prepared by embodiment 1
1h-NMR spectrogram.
Fig. 3 is Compound I I prepared by embodiment 1
1h-NMR spectrogram.
Fig. 4 is compound III prepared by embodiment 1
1h-NMR spectrogram.
Fig. 5 is compound III prepared by embodiment 1
19f-NMR spectrogram.
Fig. 6 is compound IV prepared by embodiment 1
1h-NMR spectrogram.
Fig. 7 is compound IV prepared by embodiment 1
19f-NMR spectrogram.
Embodiment
The experimental technique using in the following example if no special instructions, is ordinary method.
Following reagent all obtains from commercial channels, and be further purified processing: N, N-dimethyl-ethylenediamine (99%, Beijing lark prestige Science and Technology Ltd.), tert-Butyl dicarbonate (99%, Beijing lark prestige Science and Technology Ltd.), N, dinethylformamide (99.8%, Beijing lark prestige Science and Technology Ltd.), the bromo-1-hexene (98% of 6-, Tianjin method Moses Science and Technology Ltd.), perfluoro-hexyl iodide alkane (97%, Beijing lark prestige Science and Technology Ltd.), allyl acetate (99%, Beijing lark prestige Science and Technology Ltd.), sulfuric acid (Chemical Co., Ltd. in pairs of 95～98% Yantai City), hydrochloric acid (37%, Yantai City is Chemical Co., Ltd. in pairs).
Following reagent also obtains from commercial channels, and says single step purification processing: dibenzoyl peroxide (BPO) is purchased from can Fa Aisha (Tianjin) Chemical Co., Ltd., uses afterwards for 3 times by chloroform and recrystallizing methanol; KOH, purchased from A Faaisha (Tianjin) Chemical Co., Ltd., is ground to powder by sheet KOH, after vacuum-drying, uses; Methyl alcohol, dehydrated alcohol, anhydrous diethyl ether, normal hexane are purchased order Tianjin Fu Yu Fine Chemical Co., Ltd, are analytical pure, with reference to Purification of Laboratory Chemicals, 5
thed (Chai, C.L.L.; Armarego, W.LF., Butterwirth-Heinemann:New York, 2003.) just use after processing.
(1) preparation of Compound I
Take 0.88g (10mmol) NN-dimethyl-ethylenediamine and be dissolved in 15ml DMF, proceed to and prolong is housed (above meets CaCl
2drying tube), in tri-mouthfuls of round-bottomed flasks of 50ml of logical nitrogen tube, constant pressure funnel, then put into the water bath with thermostatic control of 25 ℃, add rotor, start stirring, pass into nitrogen deoxygenation 30min.Take 2.62g (12mmol) Boc acid anhydrides and be dissolved in 10ml DMF, then proceed in 25ml constant pressure funnel.Open cock, the Boc acid anhydrides that is dissolved in DMF is dropwise splashed in there-necked flask, 0.5h drips off, and removes constant pressure funnel.After thing reaction 1h to be mixed, the bromo-1-hexene of 245g (15mmol) 6-is dissolved in to 5ml DMF and proceeds in 10ml constant pressure funnel.Beat and rise cock, dropwise splash in above-mentioned there-necked flask, 1h drips off, and removes constant pressure funnel.After reaction mixture normal-temperature reaction 72h, stopped reaction.Removal of solvent under reduced pressure, adds anhydrous diethyl ether, and ice bath stirs 12h, separates out white solid, and suction filtration, obtains white solid powder, continues, with anhydrous diethyl ether washing three times, to obtain the Compound I that 3.01g is pure, and yield is 85.7%.
(2) preparation of Compound I I
Build the gas generating unit of HCl gas, utilize the vitriol oil and concentrated hydrochloric acid to prepare saturated HCl-diethyl ether solution 25ml.Take 2.81g (8mmol) Compound I and be dissolved in 10ml methyl alcohol, proceed to and prolong is housed (above meets CaCl
2drying tube), in tri-mouthfuls of round-bottomed flasks of 50ml of constant pressure funnel, then put into 0 ℃ of ice-water bath, add rotor, slowly stir.Pipette the saturated HCl-diethyl ether solution of 5ml, proceed to 10ml constant pressure funnel, open cock, dropwise splash in above-mentioned there-necked flask, 0.5h drips off.Then be slowly warming up to room temperature, stopped reaction after reaction 12h.Methyl alcohol, ether, HCl are removed in underpressure distillation, add anhydrous diethyl ether, and ice bath stirs 12 hours, separates out white solid, and suction filtration, obtains white solid powder, continue, with anhydrous diethyl ether washing three times, to obtain the Compound I I that 2.19g is pure, and yield is 95.1%.
(3) preparation of compound III
13.38g perfluoro-hexyl iodide alkane (30mmol), 3.03g acetic acid alkene lactone (0.3mol) are added in the 100ml four-hole bottle that spherical condensation tube, thermometer, drying tube, stirring rake are housed, be heated to 95 ℃ and keep several minutes.Add rapidly 0.145g BPO (0.6mmol), question response sharply heat release is warming up to after 160 ℃, is cooled to 120 ℃, keeps reaction 30min.Then add 35ml normal hexane and 4.05g potassium hydroxide (72mmol), back flow reaction 4h.After reaction finishes, cold filtration, filter cake washs with a small amount of normal hexane, and 77～80 ℃/40mmHg cut 7.58g is collected in filtrate decompression distillation, is colourless transparent liquid, yield 67.2% (in perfluoro-hexyl iodide alkane).
(4) preparation of compound IV
1.15g (4mmol) Compound I I, 7.52g (20mmol) compound III and 150ml dehydrated alcohol are added and prolong is housed (above meets CaCl
2drying tube), in tri-mouthfuls of round-bottomed flasks of 250ml of logical nitrogen tube, add rotor to stir, pass into nitrogen, temperature of reaction is 85 ℃, stopped reaction after reaction 6d.After reaction finishes, ethanol is removed in underpressure distillation, adds anhydrous diethyl ether, leaves standstill, and separates out to obtain yellow transparent thickness lotion, and vacuum-drying 72h, obtains the transparent thickness lotion of safran 2.57g, and productive rate is 97.3%.
(1) preparation of Compound I
As described in Example 1, difference is that the quality that changes the quality of Boc acid anhydrides into 2.40g (11mmol), the bromo-1-hexene of 6-changes 1.79g (11mmol) into, and the quality of gained Compound I is 2.85g, and yield is 81.2%.
(2) preparation of Compound I I
As described in Example 1, difference is to change the volume of saturated HCl-diethyl ether solution into 7ml, and the quality of gained Compound I I is 2.17g, and yield is 94.2%.
(3) preparation of compound III
As described in Example 1, difference is to change the quality of BPO into 0.242g (1.0mmol), and the quality of gained compound III is 7.07g, and yield is 62.7%.
(4) preparation of compound IV
As described in Example 1, difference is to change the quality of compound III into 6.02g (16mmol), and the quality of gained compound IV is 2.51g, and yield is 95.2%.
(1) preparation of Compound I
As described in Example 1, difference is that the quality that changes the quality of Boc acid anhydrides into 2.40g (11mmol), the bromo-1-hexene of 6-changes 1.63g (10mmol) into, and the quality of gained Compound I is 2.88g, and yield is 82.3%.
(2) preparation of Compound I I
As described in Example 1, difference is to change the volume of saturated HCl-diethyl ether solution into 10ml, and the quality of gained Compound I I is 2.23g, and yield is 96.8%.
(3) preparation of compound III
As described in Example 1, difference is to change the quality of BPO into 0.169g (0.7mmol), and the quality of gained compound III is 7.42g, and yield is 65.8%.
(4) preparation of compound IV
As described in Example 1, difference is to change the quality of compound III into 4.52g (12mmol), and the quality of gained compound IV is 2.43g, and yield is 92.1%.
(1) preparation of Compound I
As described in Example 1, difference is by N, the volume that the quality that the quality that the quality of N-dimethyl-ethylenediamine changes 2.64g (30mmol), Boc acid anhydrides into changes 7.21g (33mmol), the bromo-1-hexene of 6-into changes 4.90g (30mmol), DMF into changes 75ml into, the quality of gained Compound I is 8.65g, and yield is 82.4%.
(2) preparation of Compound I I
As described in Example 1, difference is that the volume that changes the quality of Compound I into 10.53g (30mmol) saturated HCl-diethyl ether solution changes 15ml into, and the volume of methyl alcohol changes 50ml into, and the quality of gained Compound I I is 8.47g, and yield is 97.1%.
(3) preparation of compound III
As described in Example 1, difference is that the quality that the volume that changes the quality of 33.45g perfluoro-hexyl iodide alkane (75mmol), 7.58g allyl acetate (75mmol), BPO into 0.36g (1.5mmol), normal hexane changes 90ml, potassium hydroxide into changes 10.12g (180mmol) into, the quality of gained compound III is 18.60g, and yield is 66.0%.
(4) preparation of compound IV
As described in Example 1, difference is that the quality that changes the quality of Compound I I into 3.45g (12mmol), compound III changes 18.06g (48mmol) into, and the quality of gained compound IV is 7.64g, and yield is 96.4%.
(1) preparation of Compound I
As described in Example 4, difference is that the volume that the quality that changes the quality of Boc acid anhydrides into 7.00g (32mmol), the bromo-1-hexene of 6-changes 5.06g (3lmmol), DMF into changes 75ml into, the quality of gained Compound I is 8.79g, and yield is 83.7%.
(2) preparation of Compound I I
As described in Example 4, difference is to change the volume of saturated HCl-diethyl ether solution into 25ml, and the quality of gained Compound I I is 8.57g, and yield is 98.2%.
(3) preparation of compound III
As described in Example 4, difference is to change the quality of BPO into 0.48g (2.0mmol), and the quality of gained compound III is 18.18g, and yield is 64.5%.
(4) preparation of compound IV
As described in Example 4, difference is to change the reaction times into 7d, and the quality of gained compound IV is 7.67g, and yield is 96.8%.
Claims (6)
1. a preparation method for fluorine carbon/hydrocarbon mixed type cation surface active monomer, wherein, compound IV is the quaternary surface active monomer that contains perfluoroalkyl and hydrocarbon hydrophobic grouping that the present invention synthesizes;
Comprise the steps:
Step (i), utilizes tert-Butyl dicarbonate to N, and the amino of N-dimethyl-ethylenediamine is protected, and amino is changed into the amide group that chemical property is more stable;
Step (ii), the N that amino has been protected by tertbutyloxycarbonyl, the bromo-1-hexene of N-dimethyl-ethylenediamine and 6-carries out quaterisation, after reaction finishes, and removal of solvent under reduced pressure, add anhydrous diethyl ether, ice bath stirs 2～12 hours, separates out white solid, suction filtration, obtain white solid powder, i.e. Compound I;
Step (iii), utilizes the ether saturated solution of hydrochloric acid to the de-tertbutyloxycarbonyl of Compound I, after reaction finishes, and removal of solvent under reduced pressure, add anhydrous diethyl ether, ice bath stirs 2～12 hours, separates out white solid, suction filtration, obtains white solid powder, i.e. Compound I I;
Step (iv), under the effect of initiator dibenzoyl peroxide, iodine and ethanoyl are then sloughed in perfluoro-hexyl iodide alkane and allyl acetate generation addition reaction under the effect of potassium hydroxide, filter, filtrate decompression distillation, collecting 77～80 ℃/40mmHg cut, is colourless liquid, i.e. compound III, 3-(perfluor n-hexyl)-1,2 epoxy prapane;
Step (v), carries out ring-opening reaction by Compound I I and compound III, and removal of solvent under reduced pressure adds anhydrous diethyl ether precipitation, obtains compound IV, is yellow thickness lotion.
2. method according to claim 1, it is characterized in that: the described N of step (i), the mol ratio of N-dimethyl-ethylenediamine and tert-Butyl dicarbonate is 1: (1.1～1.5), solvent is N, dinethylformamide, acetone, methyl alcohol or ethanol, N, N-dimethyl-ethylenediamine is 1 with the massfraction ratio of described solvent: (16～25), temperature of reaction is 25～40 ℃, reaction times is 0.5～2 hour, feeding mode is that tert-Butyl dicarbonate is dissolved in and in appropriate solvent, in 0.5～1 hour, dropwise splashes into N, in the reaction system that N-dimethyl-ethylenediamine exists, reaction is carried out under nitrogen atmosphere.
3. method according to claim 1, it is characterized in that: step (ii) finishes directly to carry out afterwards in step (i) reaction, utilize one kettle way synthetic compound I, N, the mol ratio of the bromo-1-hexene of N-dimethyl-ethylenediamine and 6-is 1: (1.1～1.3), no longer add solvent, temperature of reaction remains unchanged, reaction times is 24～72 hours, feeding mode is that bromo-6-1-hexene was dropwise splashed in the reaction system of step (i) in 0.5～1 hour, and reaction is carried out under nitrogen atmosphere.
4. method according to claim 1, it is characterized in that: the described reaction solvent of step (iii) is methyl alcohol, Compound I and with the massfraction ratio of solvent be 1: (4～7), the ether saturated solution of hydrochloric acid and the volume ratio of solvent are 1: (2.5～5), temperature is 10～25 ℃, reaction times is 6～12 hours, and feeding mode is that the ether saturated solution of hydrochloric acid was dropwise splashed in the reaction system of Compound I existence in 0.5～1 hour.
5. method according to claim 1, it is characterized in that: the mol ratio of the described perfluoro-hexyl iodide alkane of step (iv) and allyl acetate is 1: 1, by the two mix and blend, solution to be mixed keeps several minutes after being warming up to 95 ℃, add afterwards dibenzoyl peroxide, the mol ratio of dibenzoyl peroxide and perfluoro-hexyl iodide alkane is 1: (50～100), behind question response steep temperature rise to 160～170 ℃, be cooled to 120～130 ℃, keep 30～60 minutes, then in above-mentioned reaction system, add successively normal hexane and potassium hydroxide, normal hexane is solvent, and compare for (1.5～2) with the massfraction of perfluoro-hexyl iodide alkane: 1, the mol ratio of potassium hydroxide and perfluoro-hexyl iodide alkane is (2.5～3): 1, reaction times is 4～6 hours, temperature is 70～80 ℃.
6. method according to claim 1, it is characterized in that: the mol ratio of the described Compound I I of step (v) and compound III is 1: (3～5), solvent is methyl alcohol or ethanol, Compound I I is 1 with the massfraction ratio of described solvent: (100～120), temperature of reaction is 80～90 ℃, reaction times is 5～7 days, and described reaction is carried out under nitrogen atmosphere.
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